CN107771418A - A kind of copper-clad plates of high-toughness halogen-free CEM 3 - Google Patents
A kind of copper-clad plates of high-toughness halogen-free CEM 3 Download PDFInfo
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- CN107771418A CN107771418A CN201610756968.6A CN201610756968A CN107771418A CN 107771418 A CN107771418 A CN 107771418A CN 201610756968 A CN201610756968 A CN 201610756968A CN 107771418 A CN107771418 A CN 107771418A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01B—SOIL WORKING IN AGRICULTURE OR FORESTRY; PARTS, DETAILS, OR ACCESSORIES OF AGRICULTURAL MACHINES OR IMPLEMENTS, IN GENERAL
- A01B1/00—Hand tools
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2203/20—Applications use in electrical or conductive gadgets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a kind of copper-clad plates of high-toughness halogen-free CEM 3, it is made by following methods：(1) folded in the both sides of several sandwich prepregs and match somebody with somebody several veneer prepregs, obtained core, be then covered with copper foil on the one or both sides face of core, obtain semifinished sheet；(2) semifinished sheet is subjected to hot pressing compacting, produced；Wherein preparing the raw material of the glue solution for copper-clad plate of high-toughness halogen-free CEM 3 used in prepreg includes following components in parts by weight：75~120 parts of novolac epoxy resin, 300~450 parts of flame-retardant modified liquid halogen-free epoxy resin, 150~250 parts of flame-retardant modified solid-state halogen-free epoxy resins, 25~50 parts of curing agent, 0.10~0.30 part of curing accelerator and 100~200 parts of organic solvents.The copper-clad plates of high-toughness halogen-free CEM 3 not only have good heat resistance, chemical resistance, moreover it is possible to reduce pollution on the environment.
Description
Technical field
Present invention relates particularly to a kind of high-toughness halogen-free CEM-3 copper-clad plates.
Background technology
Copper-clad laminate (Copper Clad Laminate, CCL) is the main material for manufacturing printed circuit board (PCB)
Material, therefore be also any electronic product complete machine, the indispensable base electronic material of part.With the rapid development of PCB industries,
The market demand of high-performance copper coated foil plate increasingly increases, all-round developing in the green epoch, and the today to reach its maturity, except
The performances such as the heat resistance of product, TG values, CTE value receive much concern outer, and toughness, PCB processabilities, the caking property of material also become one
The individual emphasis that everybody pays close attention to, the harmony of copper-clad plate substrate performance develop into the important development for developing new copper-clad plate material
Trend.
As electronic product now is light, thin, short, small and digitized demand, miniaturization, multi-functional, high-performance and height can
By spending into mainstream development direction, PCB is caused to move towards fine pattern, high density, high multiple stratification, the line in PCB industry productions
The requirement of the techniques such as width, line-spacing, aperture, hole wall also increasingly develops towards highly integrated, high density, high multilayer direction.Such as main flow
High density interconnection laminated plates (HDI) require its micro- guide hole aperture in below 6mil, micro- guide hole orifice ring ring footpath 0.35mm with
Under, contactor density is in 130in/m2More than, wiring density is in l170in/m2More than, line width/line-spacing in below 0.1mm/0.1mm,
And high-order HDI (more than Floor 12) is then subjected to the special process such as the multiple hot pressing of high-order and more accurate careful manufacturing process will
Ask.It is especially unleaded to carry out in an all-round way and the hair at full speed of surface mounting technology (SMT) with the development of high-density installation technology
Exhibition, PCB processing with the installation of complete machine accessory, material bear repeatedly thermal shock number and temperature all conventional need is more than ever
Height, everything is all eventually converted into the huge challenge of high-performance copper coated foil plate unfailing performance.
CEM-3 (Composite Epoxy Material Grade-3) be a kind of performance level, price between CEM-1 and
Compound copper-clad laminate between FR-4, it is using epoxy resin glass fiber fabric base bonding sheet as fabric, epoxy resin Chopped Strand Mat
Base bonding sheet core material, single or double covering copper foil after hot pressing form.Because core material uses non-woven Chopped Strand Mat as strengthening material
Material, CEM-3 mechanical strength is between FR-4 and paper-based copper-coated board (CEM-1), and its bending strength is than full glass-fiber-fabric knot
The FR-4 of structure is lower slightly.Epoxy resin is used for CEM-3 preparation as the formula of glue, can improve CEM-3 toughness.To improve
The anti-flammability of epoxide resin polymer, at present to the flame-retardant modified mainly based on halogen system of epoxy resin, and this based epoxy resin
Environment can be polluted, be unfavorable for environmental protection.
The content of the invention
The technical problem to be solved in the present invention is to overcome the toughness of CEM-3 copper-clad plates in the prior art low, not environmentally
The deficiencies of, there is provided a kind of high-toughness halogen-free CEM-3 glue solution for copper-clad plate, prepreg and copper-clad plate and preparation method thereof.This
Invention mainly using the toughness of heat-resist, excellent heat conductivity novolac epoxy resin increase sheet material, selects composite curing system,
Prepare high-toughness halogen-free CEM-3 copper-clad plates.Product base material possesses good high tenacity, heat resistance, thermal conductivity, combination property also table
It is existing excellent.
The present invention is that solve above-mentioned technical problem by following technical proposals：
The invention provides a kind of high-toughness halogen-free CEM-3 glue solution for copper-clad plate, and it includes each group of following parts by weight
Part：75~120 parts of novolac epoxy resin, 300~450 parts of flame-retardant modified liquid halogen-free epoxy resin, 150~250 parts it is fire-retardant
Modified solid-state halogen-free epoxy resin, 25~50 parts of curing agent, 0.10~0.30 part of curing accelerator and 100~200 parts are organic
Solvent.
Wherein, the flame-retardant modified liquid halogen-free epoxy resin and the flame-retardant modified solid-state halogen-free epoxy resin can use
Various conventional use of flame-retardant modified halogen-free epoxy resins in the glue solution for copper-clad plate of this area.The flame-retardant modified liquid halogen-free
Epoxy resin is preferably DOPO type liquid halogen-free fire retarding epoxide resins.The flame-retardant modified solid-state halogen-free epoxy resin is preferably
For DOPO type solid-state Halogenless fire retarded epoxy resins.The performance indications of the DOPO types liquid halogen-free fire retarding epoxide resin are preferably
For：Epoxide number 320-360g/eg, the viscosity at 25 DEG C are 1800-3000mPas, phosphorus content 3.1%.The DOPO types are consolidated
The performance indications of state Halogenless fire retarded epoxy resin are preferably：Epoxide number 970-1070g/eg, the viscosity at 150 DEG C is 8000-
11000mPa·s。.
Wherein, the curing agent can be curing agent commonly used in the art, preferably dicyandiamide (DICY).
Wherein, the curing accelerator can be curing accelerator commonly used in the art, preferably diphenyl-imidazole
(2PI)。
Wherein, the solvent is solvent commonly used in the art, preferably acetone, butanone, dimethylformamide
(DMF) one or more and in propylene glycol monomethyl ether.When the solvent is acetone, butanone, dimethylformamide and propane diols first
During ether, the acetone, butanone, the weight ratio of dimethylformamide and propylene glycol monomethyl ether are preferably 1：1：6：1.
Present invention also offers a kind of preparation method of high-toughness halogen-free CEM-3 glue solution for copper-clad plate, and it includes following step
Suddenly：
(1) curing agent, the curing accelerator and the solvent are mixed, stirring is to dissolving to obtain mixture A；
(2) the mixture A is mixed with the Halogen resin, stir to obtain mixture B；
(3) under agitation, the mixture B and the novolac epoxy resin are mixed, with 2200~2800rpm's
Speed is sheared, and high-toughness halogen-free CEM-3 glue solution for copper-clad plate is produced after curing.
In the present invention, each raw material components are such as this in the preparation method of the high-toughness halogen-free CEM-3 glue solution for copper-clad plate
Glue is prepared described in component in invention.
In step (1), the method and condition of the stirring can be this area conventional method and condition.The stirring when
Between so that the curing agent and the curing accelerator are completely dissolved and are defined, preferably 3~5 hours.The rotating speed of the stirring
Preferably 900~1400rpm.
In step (2), the method and condition of the stirring can be this area conventional method and condition.The stirring when
Between so that the curing agent and the curing accelerator are completely dissolved and are defined, preferably 3~5 hours.The rotating speed of the stirring
Preferably 1000~1500rpm.
In step (3), the method and condition of the shearing can be this area conventional method and condition.The shearing when
Between preferably 1.0~2.0 hours.The rotating speed of the shearing is preferably in 2300~2700rpm steps (3), the curing
Method and condition can be this area conventional method and condition.Described curing is preferably turned with 1000~1600rpm
Speed stirring 8~12 hours；More preferably it is 9~12 hours.
Present invention also offers a kind of preparation method of high-toughness halogen-free CEM-3 copper-clad plate prepregs, it is included such as
Lower step：The high-toughness halogen-free CEM-3 glue solution for copper-clad plate is coated on reinforcing material, then dries, produces；The enhancing
Material is electronic-grade glass fiber cloth or glass felt.
Described electronic-grade glass fiber cloth and glass felt is conventional use of prepreg raw material in this area.Press
Common sense in the field, when the reinforcing material is electronic-grade glass fiber cloth, the high-toughness halogen-free CEM-3 copper-clad plates are solid with half
Change piece is veneer prepreg；When the reinforcing material is glass felt, the high-toughness halogen-free CEM-3 copper-clad plate semi-solid preparations
Piece is sandwich prepreg.
It is preferred that in the preparation of the veneer prepreg, the coating device therefor is vertical gluing machine, the painting
The speed covered is 16~23m/min；More preferably it is 18~20m/min.
It is preferred that in the preparation of the sandwich prepreg, the sandwich material coating device therefor is horizontal gluing machine；
The speed of the coating is 9~13m/min；More preferably it is 10~12m/min.
It is preferred that the temperature of the drying is 180~205 DEG C；More preferably it is 190~200 DEG C.
Present invention also offers a kind of preparation method by the high-toughness halogen-free CEM-3 copper-clad plate prepregs is made
The prepreg obtained.
Wherein, the electronic-grade glass fiber cloth can be electronic-grade glass fiber cloth commonly used in the art, preferably
For electronic-grade glass fiber cloth 7628.The glass felt can be glass felt commonly used in the art, preferably 105g glass
Felt.
The resin content of the veneer prepreg is generally 31~35wt%.The resin content of the sandwich prepreg
Generally 28~33wt%.The gel time of the veneer prepreg is generally 120~140s, and the gel time of glue is general
For 230~260s.The fluidity of the veneer prepreg is generally 18~24%.The fluidity of sandwich prepreg is generally
22~30%.The fugitive constituent of the veneer prepreg is less than 0.5%, and such as 0.3%, the volatile matter of the sandwich prepreg
It is less than 0.5%, such as 0.3%.By common sense in the field, sandwich prepreg need not determine gel time.
Present invention also offers a kind of preparation method of high-toughness halogen-free CEM-3 copper-clad plates, it comprises the following steps：
(1) folded in the both sides of several sandwich prepregs and match somebody with somebody several described veneer prepregs, obtain core, so
Copper foil is covered with the one or both sides face of core afterwards, obtains semifinished sheet；
(2) semifinished sheet is subjected to hot pressing compacting, produces copper-clad plate.
In the present invention, the folded method for stacking prepreg with for copper-clad plate preparation technology field routine, it is usually
With size and shape identical, several prepregs are neatly stacked, i.e. what each side of prepreg was all alignd stacks.This
It is described folded with not needing pressure in invention, it is described folded with typically following four big principles：Gel content high level matches with low level principle, cloth type one
Cause principle, symmetrical configuration principle and left and right collocating principle.
In step (2), the method and condition of the hot pressing compacting can be this area conventional method and condition.By this area
General knowledge, after configuring steel plate and brown paper successively on copper foil before hot pressing compacting, then hot pressing compacting is carried out, after hot pressing compacting,
Remove brown paper and steel plate.The number of the brown paper is generally 18~20.
The pressure of the hot pressing compacting is preferably 20~34kg/cm2；More preferably it is 27~32kg/cm2。
The temperature of the hot pressing compacting is preferably 130~200 DEG C；More preferably it is 160~190 DEG C.
The time of the hot pressing compacting is preferably 130~150min.
In the present invention, the preparation method of the high-toughness halogen-free CEM-3 copper-clad plates, follow-up sharp processing is typically also carried out
And inspection process, to ensure the quality of product.
Present invention also offers a kind of high tenacity as obtained by the preparation method of the high-toughness halogen-free CEM-3 copper-clad plates
Halogen CEM-3 copper-clad plates.
It on the basis of common sense in the field is met, above-mentioned each optimum condition, can be combined, it is each preferably real to produce the present invention
Example.
Agents useful for same and raw material of the present invention are commercially available.The positive effect of the present invention is：
1st, this has been used in glue of the invention, prepreg and the preparation method of high-toughness halogen-free CEM-3 copper-clad plates
The glue of invention, and their preparation method technique is simple, cost is low, consistent, fraction defective is low, the controllability of technique is strong,
Suitable for producing in enormous quantities.
2nd, high-toughness halogen-free CEM-3 copper-clad plates of the invention meet production technologies of the downstream PCB to sheet material toughness, comprehensive
Can be good, especially Halogen, toughness, heat-resisting, mechanical strength, thickness evenness are preferable, such as bromine content (PPm), less than 500,
Industry is fully meet than standard value 900；T-288 ＞ 60min, than general more than high 50 times of FR-4 halogen-free copper-clad plates.The present invention's
High-toughness halogen-free CEM-3 copper-clad plates are not stratified, non-foaming in thermal stress test.
Brief description of the drawings
Fig. 1 is the sample photo of the falling weight impact test of effect example 1.Wherein, left side is to cover copper made from embodiment 3
Plate；Right side is similar common CEM-3 copper-clad plates.
Embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to described reality
Apply among a scope.The experimental method of unreceipted actual conditions in the following example, conventionally and condition, or according to business
Product specification selects.
Embodiment 1
First, high-toughness halogen-free CEM-3 glue solution for copper-clad plate preparation methods are planted：
Composition of raw materials：
Resin：100 parts of novolac epoxy resin, 400 parts of flame-retardant modified liquid halogen-free epoxy resin, flame-retardant modified solid-state Halogen
200 parts of epoxy resin；Here modified epoxy is DOPO type Halogenless fire retarded epoxy resins, name of product：DOPO types, epoxy
Value：8.3-9.4 (Eq/kg), viscosity 27 DEG C (mPas)：2000-5000；Here flame-retardant modified solid epoxy resin is DOPO
Type Halogenless fire retarded epoxy resin, name of product：DOPO types, epoxide number：970-1070 (g/eg), viscosity 150 DEG C (mPas)：
8000-11000；
Curing agent：40 parts of dicyandiamide (DICY)；
Curing accelerator：0.20 part of 2- phenylimidazoles (C-2 substitutions)；
Solvent：150 parts of organic solvent (acetone：Butanone：DMF：Propylene glycol monomethyl ether=1：1：6：1).
Preparation method：Curing agent, accelerator and solvent are mixed, 4 hours are stirred completely to dissolving with 1000rpm rotating speed
Obtain mixture A；(2) mixture A and flame-retardant modified liquid halogen-free epoxy resin, flame-retardant modified solid-state halogen-free epoxy resin are mixed
Close, 5 hours are stirred to the mixture B that stirs to obtain with 1300rpm rotating speed；(3) under agitation, by mixture B and phenol
Formaldehyde epoxy resin mixes, and with 2300rpm rotating speed high-speed stirred 2 hours, is stirred 10 hours and is cured with 1000rpm rotating speed
After produce, the gel time of glue is 230s.
2nd, high-toughness halogen-free CEM-3 copper-clad plates
Preparation method：1. glue：Using gluing machine in 2 electronic-grade glass fiber cloths 7628 (doing panel overlay material) and 1
Open and above-mentioned obtained high-toughness halogen-free CEM-3 glue solution for copper-clad plate is coated on 105g glass felts (doing sandwich)；The baking of gluing machine
Box temperature degree is 190 DEG C, and the speed of facing material gluing is 20m/min, obtains 2 prepregs, the resin content of the prepreg
For 32wt%, the gel time of the prepreg is 130s, and the fluidity of the prepreg is 22%, the volatilization of the prepreg
Part is 0.3%.The speed of sandwich material gluing is 11m/min, obtains 1 prepreg, the resin content of the prepreg is
29wt%, the fluidity of the prepreg is 26%, and the fugitive constituent of the prepreg is 0.3%；
2. lamination：3 prepregs are folded and matched somebody with somebody, it is two-sided to be all covered with copper foil, obtain semi-finished product；
3. described semi-finished product are carried out into hot pressing compacting, the temperature of hot pressing compacting is 190 DEG C, and the pressure of hot pressing compacting is
30kg/cm2, the time of hot pressing compacting is 143min, is produced.
Gained copper-clad plate is subjected to performance measurement, the results are shown in Table 1.
The performance parameter of copper-clad plate in the embodiment 1 of table 1
From table 1, the copper-clad plate combination property obtained by embodiment 1 is good.
Embodiment 2
First, high-toughness halogen-free CEM-3 glue solution for copper-clad plate preparation methods are planted：
Composition of raw materials：
Resin：80 parts of novolac epoxy resin, 300 parts of flame-retardant modified liquid halogen-free epoxy resin, flame-retardant modified solid-state Halogen
150 parts of epoxy resin；Here fire-retardant modified epoxy resin is DOPO type Halogenless fire retarded epoxy resins, name of product：DOPO types,
Epoxide number：8.3-9.4 (Eq/kg), viscosity 27 DEG C (mPas)：2000-5000；Here flame-retardant modified solid epoxy resin is
DOPO type Halogenless fire retarded epoxy resins, name of product：DOPO types, epoxide number：970-1070 (g/eg), 150 DEG C of (mPa of viscosity
s)：8000-11000；
Curing agent：30 parts of dicyandiamide (DICY)；
Curing accelerator：0.20 part of 2- phenylimidazoles (C-2 substitutions)；
Solvent：120 parts of organic solvent (acetone：Butanone：Dimethylformamide：Propylene glycol monomethyl ether=1：1：6：1).
Preparation method：Curing agent, accelerator and solvent are mixed, 4 hours are stirred completely to dissolving with 1000rpm rotating speed
Obtain mixture A；(2) mixture A and flame-retardant modified liquid halogen-free epoxy resin, flame-retardant modified solid-state halogen-free epoxy resin are mixed
Close, 5 hours are stirred to the mixture B that stirs to obtain with 1300rpm rotating speed；(3) under agitation, by mixture B and phenol
Formaldehyde epoxy resin mixes, and with 2500rpm rotating speed high-speed stirred 2 hours, is stirred 9 hours and is cured with 1000rpm rotating speed
After produce, the gel time of glue is 245s.
2nd, high-toughness halogen-free CEM-3 copper-clad plates
Preparation method：1. glue：Using gluing machine in 2 electronic-grade glass fiber cloths 7628 (doing panel overlay material) and 1
Open and above-mentioned obtained high-toughness halogen-free CEM-3 glue solution for copper-clad plate is coated on 105g glass felts (doing sandwich)；The baking of gluing machine
Box temperature degree is 195 DEG C, and the speed of facing material gluing is 20m/min, obtains 2 prepregs；The resin content of the prepreg is
32wt%, the gel time of the prepreg is 133s, and the fluidity of the prepreg is 21%, the fugitive constituent of the prepreg
For 0.3%.The speed of sandwich material gluing is 12m/min, obtains 1 prepreg, and the resin content of the prepreg is 30wt%,
The fluidity of the prepreg is 27%, and the fugitive constituent of the prepreg is 0.3%.
2. lamination：6 prepregs are folded and matched somebody with somebody, it is two-sided to be all covered with copper foil, obtain semi-finished product；
3. described semi-finished product are carried out into hot pressing compacting, the temperature of hot pressing compacting is 195 DEG C, and the pressure of hot pressing compacting is
30kg/cm2, the time of hot pressing compacting is 145min, is produced.Gained copper-clad plate is subjected to performance measurement, the results are shown in Table 2.
The performance parameter of the copper-clad plate of the embodiment 2 of table 2
From table 2, the copper-clad plate combination property obtained by embodiment 2 is good.
Embodiment 3
First, high-toughness halogen-free CEM-3 glue solution for copper-clad plate preparation methods are planted：
Composition of raw materials：
Resin：120 parts of novolac epoxy resin, 450 parts of flame-retardant modified liquid halogen-free epoxy resin, flame-retardant modified solid-state Halogen
250 parts of epoxy resin；Here fire-retardant modified epoxy resin is DOPO type Halogenless fire retarded epoxy resins, name of product：DOPO types,
Epoxide number：8.3-9.4 (Eq/kg), viscosity 27 DEG C (mPas)：2000-5000；Here flame-retardant modified solid epoxy resin is
DOPO type Halogenless fire retarded epoxy resins, name of product：DOPO types, epoxide number：970-1070 (g/eg), 150 DEG C of (mPa of viscosity
s)：8000-11000；
Curing agent：50 parts of dicyandiamide (DICY)；
Curing accelerator：0.30 part of 2- phenylimidazoles (C-2 substitutions)；
Solvent：200 parts of organic solvent (acetone：Butanone：Dimethylformamide：Propylene glycol monomethyl ether=1：1：6：1).
Preparation method：Curing agent, accelerator and solvent are mixed, 4 hours are stirred completely to dissolving with 1000rpm rotating speed
Obtain mixture A；(2) mixture A and flame-retardant modified liquid halogen-free epoxy resin, flame-retardant modified solid-state halogen-free epoxy resin are mixed
Close, 4 hours are stirred to the mixture B that stirs to obtain with 1300rpm rotating speed；(3) under agitation, by mixture B and phenol
Formaldehyde epoxy resin mixes, and with 2400rpm rotating speed high-speed stirred 2 hours, is stirred 12 hours and is cured with 1600rpm rotating speed
After produce, the gel time of glue is 260s.
2nd, high-toughness halogen-free CEM-3 copper-clad plates preparation method：1. glue：Using gluing machine in 2 electronic-grade glass
Above-mentioned obtained high-toughness halogen-free CEM-3 is coated on cloth 7628 (doing panel overlay material) and 1 105g glass felt (doing sandwich)
Glue solution for copper-clad plate；The oven temperature of gluing machine is 200 DEG C, and the speed of facing material gluing is 21m/min, obtains 2 prepregs；
The resin content of the prepreg is 33wt%, and the gel time of the prepreg is 135s, and the fluidity of the prepreg is
20%, the fugitive constituent of the prepreg is 0.3%.The speed of sandwich material gluing is 11m/min, obtains 1 prepreg, should be partly solid
The resin content for changing piece is 31wt%, and the fluidity of the prepreg is 29%, and the fugitive constituent of the prepreg is 0.3%.
2. lamination：6 prepregs are folded and matched somebody with somebody, it is two-sided to be all covered with copper foil, obtain semi-finished product；
3. described semi-finished product are carried out into hot pressing compacting, the temperature of hot pressing compacting is 185 DEG C, and the pressure of hot pressing compacting is
31kg/cm2, the time of hot pressing compacting is 148min, is produced.
Effect example 1
The high-toughness halogen-free CEM-3 copper-clad plates of embodiment 3 are subjected to performance detection, its main performance result see the table below table 3
It is shown.Other embodiment product effect is similar.Detection method is common detection methods.
The performance parameter of the copper-clad plate of the embodiment 3 of table 3
Falling weight impact test (toughness test experiment)
Laboratory apparatus：ISO Impact Tester, brand BYK Gardner, model 5512；
Laboratory sample：Base material thickness 1.0mm~1.1mm, 7628 × 1+105g of matrix structure felt × 1+7628 × 1ply；
Experimentation：Sample after etching is installed by instrument requirements, will drop hammer the position that is fixed on 20mm height, make it
Freely falling body hits material, and the cross crack caused by shock material that drops hammer is more clear, illustrates toughness of material, Punch effects more
It is good.Fig. 1 is the sample photo of falling weight impact test.It will be seen from figure 1 that copper-clad plate (Fig. 1 obtained by the embodiment of the present invention 3
The left side) toughness be substantially better than the similar common CEM-3 copper-clad plates material in market (on the right of Fig. 1).
Claims (10)
1. a kind of high-toughness halogen-free CEM-3 copper-clad plates, it is characterised in that it is made by following methods：
(1) folded in the both sides of several sandwich prepregs and match somebody with somebody several veneer prepregs, core is obtained, then the one of core
Copper foil is covered with side or two sides, obtains semifinished sheet；
(2) semifinished sheet is subjected to hot pressing compacting, produced；
Wherein, the sandwich prepreg is made by following methods：High-toughness halogen-free CEM-3 copper-clad plates are coated on glass felt to use
Glue, then dry, produce；
The veneer prepreg is made by following methods：High-toughness halogen-free CEM-3 is coated on electronic-grade glass fiber cloth to cover
Copper coin glue, is then dried, and is produced；
The high-toughness halogen-free CEM-3 glue solution for copper-clad plate, it is made by following raw materials, and the raw material includes following weight parts
Component：75~120 parts of novolac epoxy resin, 300~450 parts of flame-retardant modified liquid halogen-free epoxy resin, 150~250 parts of resistances
The modified solid-state halogen-free epoxy resin of combustion, 25~50 parts of curing agent, 0.10~0.30 part of curing accelerator and 100~200 parts have
Solvent.
2. high-toughness halogen-free CEM-3 copper-clad plates as claimed in claim 1, it is characterised in that the flame-retardant modified liquid halogen-free
Epoxy resin is DOPO type liquid halogen-free fire retarding epoxide resins；
And/or the flame-retardant modified solid-state halogen-free epoxy resin is DOPO type solid-state Halogenless fire retarded epoxy resins；
And/or the curing agent is dicyandiamide；
And/or the curing accelerator is diphenyl-imidazole；
And/or the organic solvent is the one or more in acetone, butanone, dimethylformamide and propylene glycol monomethyl ether.
3. high-toughness halogen-free CEM-3 copper-clad plates as claimed in claim 1, it is characterised in that the acetone, butanone, dimethyl
The weight of formamide and propylene glycol monomethyl ether ratio is 1：1：6：1.
4. the high-toughness halogen-free CEM-3 copper-clad plates as described in any one of claims 1 to 3, it is characterised in that the DOPO types liquid
The performance indications of state Halogenless fire retarded epoxy resin are：Epoxide number 320-360g/eg, the viscosity at 25 DEG C is 1800-3000mPa
S, phosphorus content 3.1%；
And/or the performance indications of the DOPO types solid-state Halogenless fire retarded epoxy resin are：Epoxide number 970-1070g/eg, 150 DEG C
Under viscosity be 8000-11000mPas.
5. the high-toughness halogen-free CEM-3 copper-clad plates as described in any one of claims 1 to 3, it is characterised in that the high tenacity without
Halogen CEM-3 glue solution for copper-clad plate, is made by following method：
(1) curing agent, the curing accelerator and the solvent are mixed, stirring is to dissolving to obtain mixture A；
(2) the mixture A is mixed with the Halogen resin, stir to obtain mixture B；
(3) under agitation, the mixture B and the novolac epoxy resin are mixed, with 2200~2800rpm speed
Sheared, high-toughness halogen-free CEM-3 glue solution for copper-clad plate is produced after curing.
6. high-toughness halogen-free CEM-3 copper-clad plates as claimed in claim 5, it is characterised in that in step (1), the stirring
Time is 3~5 hours；
And/or in step (1), the rotating speed of the stirring is 900~1400rpm；
And/or in step (2), the time of the stirring is 3~5 hours；
And/or in step (2), the rotating speed of the stirring is 1000~1500rpm；
And/or in step (3), the time of the shearing is 1.0~2.0 hours；
And/or in step (3), rotating speed more 2300~2700rpm of the shearing；
And/or in step (3), described curing is to be stirred 8~12 hours with 1000~1600rpm rotating speed.
7. high-toughness halogen-free CEM-3 copper-clad plates as claimed in claim 1, it is characterised in that the electronic-grade glass fiber cloth
For electronic-grade glass fiber cloth 7628；
And/or the glass felt is 105g glass felts；
And/or in the preparation of the veneer prepreg, the coating device therefor is vertical gluing machine；
And/or in the preparation of the sandwich prepreg, the coating device therefor is horizontal gluing machine.
8. high-toughness halogen-free CEM-3 copper-clad plates as claimed in claim 7, it is characterised in that in the veneer prepreg
In preparation, the speed of the coating is 16~23m/min, preferably 18~20m/min；
And/or in the preparation of the sandwich prepreg, the speed of the coating is 9~13m/min, preferably 10~
12m/min；
And/or the speed of the sandwich material coating is 9~13m/min；Preferably 10~12m/min.
9. the high-toughness halogen-free CEM-3 copper-clad plates as described in any one of claim 7 or 8, it is characterised in that the veneer half is solid
The resin content for changing piece is 31~35wt%；The gel time of the veneer prepreg is 120~140s；The veneer half is solid
The fluidity for changing piece is 18~24%；The volatile matter of the veneer prepreg is less than 0.5；
And/or the resin content of the sandwich prepreg is 28~33wt%；The fluidity of the sandwich prepreg is 22
~30%；The volatile matter of the sandwich prepreg is less than 0.5.
10. preparation method as claimed in claim 1, it is characterised in that the pressure of step (2) hot pressing compacting for 20~
34kg/cm2；Preferably 27~32kg/cm2；
And/or the temperature of the hot pressing compacting is 130~200 DEG C, preferably 160~190 DEG C；
And/or the time of the hot pressing compacting is 130~150min.
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| CN201610756968.6A CN107771418B (en) | 2016-08-29 | 2016-08-29 | High-toughness halogen-free CEM-3 copper-clad plate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111703171A (en) * | 2020-05-09 | 2020-09-25 | 江苏诺德新材料股份有限公司 | Processing production process of 5G high-frequency microwave copper-clad plate |
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